Catalytic Ring-Opening Polymerisation of Cyclic Ethylene Carbonate: Importance of Elementary Steps for Determining Polymer Properties Revealed via DFT-MTD Simulations Validated Using Kinetic Measurements.

The production of CO 2 -containing polymers is still very demanding in terms of controlling the synthesis of products with pre-defined CO 2 content and molecular weight. An elegant way of synthesising these polymers is via CO 2 -containing building blocks, such as cyclic ethylene carbonate (cEC), via catalytic ring-opening polymerisation. However, to date, the mechanism of this reaction and control parameters have not been elucidated. In this work, using DFT-metadynamics simulations for exploiting the potential of the polymerisation process, we aim to shed more light on the mechanisms of the interaction between catalysts (in particular, the catalysts K 3 VO 4 , K 3 PO 4 , and Na 2 SnO 3 ) and the cEC monomer in the propagation step of the polymeric chain and the occurring CO 2 release. Confirming the simulation results via subsequent kinetics measurements indicates that, depending on the catalyst's characteristics, it can be attached reversibly to the polymeric chain during polymerisation, resulting in a defined lifetime of the activated polymer chain. The second anionic oxygen of the catalyst can promote the catalyst's transfer to another electrophilic cEC monomer, terminating the growth of the first chain and initiating the propagation of the new polymer chain. This transfer reaction is an essential step in controlling the molecular weight of the products.